Propyl mercaptan → HCID 59516113, compound

HRID 1160543Notes

Reaction equation

HRID 1160543 reaction equation
[C:1]([O:5][C:6]([C:8]1[CH:9]=[N:10][N:11]([CH2:14][C:15]2[CH:20]=[CH:19][C:18]([C:21]([O:23][CH3:24])=[O:22])=[CH:17][CH:16]=2)[C:12]=1Cl)=[O:7])([CH3:4])([CH3:3])[CH3:2].C(=O)([O-])[O-].[K+].[K+].[CH2:31]([SH:34])[CH2:32][CH3:33].CCOC(C)=O>C(#N)CCC>[C:1]([O:5][C:6]([C:8]1[CH:9]=[N:10][N:11]([CH2:14][C:15]2[CH:20]=[CH:19][C:18]([C:21]([O:23][CH3:24])=[O:22])=[CH:17][CH:16]=2)[C:12]=1[S:34][CH2:31][CH2:32][CH3:33])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 7848Propyl mercaptan2×HCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 59516071HCID 59516071, compound

Product 1

HCID 59516113HCID 59516113, compoundYield 62.1%

Reagents, catalysts & solvents 1

HCID 8008ButyronitrileSolvent2×

Conditions

Temperature
180 °C

Procedure

5-Chloro-1-(4-methoxycarbonyl-benzyl)-1H-pyrazole-4-carboxylic acid tert-butyl ester (Intermediate#48) (397 mg, 1.13 mmol) was dissolved in butyronitrile (8 mL), potassium carbonate (470 mg, 3.40 mmol) and propanethiol (128 ul, 1.41 mmol) were added and the mixture heated to reflux and stirred at this temperature over night. The reaction mixture was transferred to a microwave vial (using ˜5 ml extra Butyronitrile to ensure complete transfer), a further 3 eq of propane thiol was added and the reaction was heated at 180° C. for 4 hours. EtOAc (˜50 mL) was added and the mixture washed with water (3ט20 mL) and brine (˜20 ml) then dried (MgSO4), filtered and evaporated to give a yellow oil. Oil purified by column chromatography (12 g Si, eluting with 10 to 50% EtOAc in IH) to yield the title compound as a yellow oil (274 mg, 62%).

Workup

  1. temperaturethe mixture heated
  2. temperatureto reflux
  3. washthe mixture washed with water (3ט20 mL) and brine (˜20 ml)
  4. dry with materialthen dried (MgSO4)
  5. filtrationfiltered
  6. customevaporated
  7. customto give a yellow oil
  8. customOil purified by column chromatography (12 g Si, eluting with 10 to 50% EtOAc in IH)

Sources & evidence

ORD record
ord-565b2dc99f3b4e4eadd5294a6f822bcf
Source dataset
uspto-grants-2010_10
Patent number
US07816391B2

Reaction notes

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